Apparatus for electrolytic deposition of metals.



358341'1 v -PATBNTED JUNBIzs. 1,907.-- HJG. HARRISQN & J. DAY. APPARATUS PoR BLBQTROLYTIG nBPosITIoN of' METALS.

i APPLICATION FILED AUG. 7, 1902.

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" No. 853.341. y 1

PATRNTRD JUNRW25, 1907,' 11,0. HARRISON R J. DAY. f APPARATUS FOR RLRGTROLYTIG DRPO'SITION 0F METALS.v

APPLICATION FILED AUG. 7,-1902.

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PATBNTBD JUNE 25. 1907 H. c.. HARRISON & J'. DAY., APPARATUS POR ELEGTROLYTIC DEPOSITION 0F METALS.

APPLIoAJTIoN FILED AUG. '7. 1902..

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.I ous depositwith smooth surface is obtained.

UNITED STATES -IPATFNT OFFICE.

' 'HERBERT CHAMPION HARRISON, oF LONDON, AND JOSEPH DAY, oF WESToN-sUPER-MARE, 4 131\IGLA ND; SAID DAY ASSIGNOR To 'SAID HARRISON.

APPARATUS FOR ELEoT-Pzolnrrlc` DElPoslTloN oF METALS.

To rL//l 14j/1,0m t may concern:

'Be known that we, HERBERT CHAMPION" certain'new and' useful In rovements in the Electrolytic Deposition o Metals, of which.

the following is a specification.

vOur invention rel-ates lto improvements 1n the electrolytic deposition of metals whereby though a high current density (involving correspondingly rapid deposition) v is employed, nevertheless a tough vand homogene- In" the 'electrolytic deposition of metals from solutions of their salts particularly copemployed in the per it is found thatl if the current density employed greatly exceeds' thatwhich is usually processes at present in use for the deposition of `suchxmetal from such solution the surface of the deposited metal deteriorates and at the same time the charyacter of the depositedmetal changes becommg at first less dense and'oftenbrittle, ex-

hibiting a coarse fracture when broken, and

f that finally `if the current densitybe sufIivas ciently increased it the metal is deposited in a muddy incoherent form. Furthermore the deposited metal even if deposited at sufficiently low current density to be in'a coherent form is usually in the shape of flatv bar s or plates which will iirst have to be re-cast before the metal canbe lused commercially for making vtubes sheet or wire. l

' Many attempts have been made to produce 'a finished article yof copper by one electrolytic process at a higher current density than that usually employed. Most of these have depended upon the vmechanical consolidation (by mechanicalpressure) of the metal during deposition'while others aimed at obtaining dense tough and. smooth deposits from the beginningwithout mechanical consolidation. However either llthe deposits have been found to be inferior and faulty in charaeterorthe processes have been attended by so much practical difficulty that hitherto the problem'hasnot been satisfactorily and economically solvedcommeroially.

Now according to our invention we are enabled to employ current densities greatly in,

. VSpecicatiezzfof ,Letters1Patent. 4 Application iledwelugust 7.1902- Serial Nuorlliiol.`

-or the tube can` gwith the same or immediately 'with clean and fresh unim Patented June 25, 1907 excess of thoseusually employed and at the same time to obtain a tough smooth and homogeneous deposit in the form of a tube Y v 'which is itself at once of commercial-utility (without havin to be re-cast unless desired) e cut so as togive a sheet. VAccording r to our invention we effect a continual, complete and' rapid .renewahby displacement and re lacement, of the layer of electrolyte imme iately contiguous to a cathode lcircular in cross section and over the whole surface of, the said cathode (i. e. throughout the -whole length-thereof and all round same) but more particularly over vthose parts exposed mostv directly to the action of the anode t'. e. where the resistance between the electrodes isl leastl andv conseyquently the current density greatest. In

other words wel create*- a high differential velocity between the surface of the saidcathode and the layer of electrolyte in contact contiguous thereto and We continually renew this layer overishedelectrolyte. lFor we have foun that it is due to the impoverishing ofthis'layer of electrolyte by a current of high density acting for any prolonged period and the non-renewal ra idly and continuouslyand completely of said impoverishedlayer that bad metal is de-l posited. To. renew the whole contents of the depositing vatsufiiciently rapidly to secure thecontinual'r'enewal of this extremely thin layer is obviously impracticable and unnecessary, as is also to renew the whole volume of electrolyte between the anode and -the cathode, since, except when deposits of extreme thinnes's are required, the anode to four inches) from the cathode,'this distance varying according to the current denmust be at a workable distance (say one inch IOO posit is better if the surface of the cathode is highly polished. We `renew the layer `of electrolyte, contifuous Vto the cathode by means of jets' of? electrolyte Adirected tanl gentially tothe surface of cathode-.. ets

lov

of electrolyte so employed most effectually displace 4and renew l the*y `liquid iny the ex treinelyw small cavities or inequalities in or on the 'surface of anelec'trolytic deposit. The jets used by us maybe obtained by surroundingthe cathode with vertical spraypipes of aiin'terial, such Aas vulcanite, which -does not conduct electricity and which is not attacked by4 fthe solution employed. f The'- spray-pipes are arranged parallel With..the

surface'of `the cathode to be deposited upon and are bored at intervals or so formed, as to .y emit theelectrolyte in a direction tangential tqthe,surlacelofglthe cathode.` The sprayplpes are, kept constantly'supplied with elec,-y trolyte .under suitable 'pressure for instance eitherb'y" a puinpjor` by gravity from vat pjlacedfata suitable level and supplied by-a pump. We have found that one jet..-Will eiifecltually renew this layer of lelectrolyte A. caselof va. jet ,tangentially irripinging. 301

only over agiven area and most effectually only.; close to where the jet impinges upon the circular cathode tangentially. AIf di.-l re'ctefd radially uponk the circular cathode lat theactual point o f impact the'electrolytejis very l effectuallv renewed but the efficiency,

of. renewal fallszoffjmore,rapidly than in `the various diameters of hole *ornozzle for the projection of a tangentially in ipinging jet' of electrolytey the width ofband influenced has been determined experimentally by us and.l the iniiuence lof the jet was found to fall off from the'center to the edge 'of :the band inn fluenced'.. We therefore. bore or form the pipes so that the space between two adjacent jets is preferably half the width of the band infiuenced. By this means the effect of'ltwo adjacent jets is super-imposedwhere the influence of each tends to diminish. j 4 Now eachA complete spray-pi e will influence a deiini'te fraction of t ie circum-l. A ference of theL cathode of cylindrical or con ical .or other. `circular form in cross`-`s`ection Ay sufficient.l ynuvnnber of spray-pipes must therefore be employed all round the cathode and extending from end to end thereof to ine.

'fluence the whole surface of such cathode.

,'[lhe vanode is made of bars or groups of barlsf(either consisting of the metal to be deposited o'r-,in cases where the deposit of metal onthe cathode is to ,be obtained from salts in solution inthe bath without the sis* of a'substance not liable to'be attacked by the electrolyte) arranged around the cathode and so placedvasfto be directly opposite andv i parallel to the line of impact of the ets from each'sprayfpipe respectively. We thus sethe bands upon the surface of the exposed to the greatest current denare, joincident withthe bands where the j' jets fronigea'ch spray-pipe impinge. 6 5

obtain the best results by 'tration or otherwise.

metallof the anodedissolving in the bathslowly' rotating the cathode about Lits own axis so as to insure all parts of the cathode being evenly coated.', l f' i f.

lBy this invention we secure au effective and continual renewal of thelayer of electrolyte immediately contiguous to the cathode land at the same timela*,partiallyllocalized action of the current sotliatv the greatest current densities are distributed over those parts of the cathode surface subjected--tof'the greatest action .of the jets, the current density falling off as the effect producedby the jets falls off from the point `of their greatest. efiiciency. l,We also -secure that the solution around theY cathode isv concentratedy while after it has been impoverished by the curlrent itis forced to. pass the anode without again coming .into contact with the cathode until its strengtlrhas been renewed.

.The closer thelanode is lto the cathode the lower becomes the resistance of the depositing vat and the lesslthe electro1notive force necessary to work at any particular current Adensity. But .the closer the anode Vto the cathode the sooner the surface jof the deposit will deteriorate.. ,in smoothness so that the thicker the deposit required .the greater must be the distance between the anode and the cathode, always remembering that each anode bar or group of bars however near or yremote from the cathode should be directly posite thejsphere of greatest influence of of v t ie corresponding spray-pipe.

v Raising the temperature of the electrolyte will reduce the resistance of the depositing .vatrand so reduce the electro-motive force necessary.

It will be found advantageous in most' 'cases to use the strongest solution possible; and, where acidled, a strongly acid one; f avolding 1n every case a solution so strong as the drawings hereunto annexed.

Figure l is a view in side elevation of apparatus according'to and for carrying out the present invention. Fig. 2 is plan thereof. Figi 3 is local plan-fon an enlarged scale-of the vessel with the cathode and anode therein. Fig. 4 is vertical sectionaljview on line 4 4 Fig. 3. f

'a is suitable vat or vessel adapted to hold the electrolyte.

b is the vertical spindle journaled in bracka is the brush.

etsc cland above. the

said cathode is immersed in the'electrolyte;

e e are series'of vertical pipes spaced-apart ejquidistant from one another and advantageously disposed conoentrically around the cathode and parallel to the longitudinal. di-' .5 rection thereof; these'vertical'pipes e (which are closed at their upper ends) or nozzles (see Fig. 4) i'n such position and in suchwise' that the said nozzles will direct .the

`jets z issuing therefromin a/direction tangential to the su'rface'of the cylindrical cathode scribed.

ses

-each s uch vertical be readily ascertained (in the to the 'surface rangement shown in the drawings th'e electrolyte overiioWing 'the eleetrolyte through the j ed to give the re :s-#see Fig. '3. For example in practice we have found `that We'can successfully carry cathode of -or about 3 inches 'diameter b y em# .ploying verticalpipes located at or about 2% inches from the center of such cathode, and spaced-apartat or about 2% inches-from one another concentrically allround such cathode,

of each of the. series of holes in pipe maybe 3/32 of an inch and such holes may be provided at intervals of anfinch from one another through-4 out the. vertical length of the pipe; but in other cases wi-thdiifering conditions then the distance of the` verticalpipes from one anand the size other 'and from the cathode fand the size of the holes insaid verticalpipes and the distance apart' of said holes wil va ry -according 'case which can manner hereinbefore described) by any person skilled in the art and need not therefore be here further delto the requirements imeach The electrolyte is forced by any suitable pipes e and issues therefrom in the form of jets zal] round and tangential of the cathode w; in the-arfrom the spout f of the vessel aliows through the filters g g1 into the suction' tank 7L and then is withdrawn through the suction pipe *i by means of any suitable pump (such as the centrifugal pump j) which may'either force the electrolyte direct into or said pum may force pipe into a' reservoiror tank Z at anysuitab'le height adaptuired pressure to the jets z from which ta. the electrolyte passes ",throughxthe connecting pipe m and' through I thex'plipenleading to the chamber'o from 6 0 Wlli atten the electrolyte is ,foreed into the verticalpipe's e.

i The anode ofqcppe-r (or other suitable metal"y adapted y to beelectrolytically deposited) may beof'any suitable'form or shapebut in the casefof copperwe have found a series provided with means to slowly rotate said spindle such as the pulley b1 and means (such as the -eye b2) by which to bodily raise the cathode onsaid'vertical spindle b.r

vat and to lower the spindle until are provided' at frequent intervals along same with holes metal or metals to points` of the'cathode @f each said group of copper lbarsand 'all the sald groups coupled up by the connections g thus the electric current liows throughthe connections :g and through each ofthe groups of copper bars same being all .in electricalv connection andl forming the anode.

Although our invention is signed for the electrolytic deposition of copper Iand simultaneous refining thereof yet 1t may be carried into practice with any other j By the use of` the expression "tangentiaP 8 5 or tangentially herein we -do not `wish to -be understood to confine ourselves to the strict mathematical definition of a tangential lineas in practice we find it advantageous to direct the jets toward a point on the cath-v ode slightly nearer tov the pipe discharging such jets lthan the point where the true tangential line from said pipe would touch said cathode but always so as not to direct the. jets. radially against said cathodelin other words we find it advantageous to direct the .jets toward the cathode in` adirection (toward the cathode) between the radial lline and tangential' line formed from said discharging pipeto the cathode.

aving now described our invention Wha we claim as new and desire to secure by Letters Patent of the United States is 1. lIn the electrolytical de osition of metals upon a cathode, the com ination with a cathode, of a plurality of anodesarranged around the cathode in elements consisting of one or more anode bars, and means parallel to the axis of the cathode for producing jets .Of electrolyte adapted to impinge against the cathode' so. that the greatest action ofthe jts v upon the cathode will take place at those nearest theelements of the anode where the resistance between Athe electrodes is least and,` consequently, the cur- .rent density greatest. 4 2. Inl the electrolytical*deposition of metals, the combination with a vertically-mountved cathode, of a plurality of perforated pipes parallel to the axis :of the cathode, disposed equidistant from one another, and disposed concentrically around and spaced apart equally all around said cathode, issue jets of electrolyte'so -as to impinge in a tangential direction against the surface of the cathode all around the latter-andthrough' out lthe length thereof, and a plurality of anod'es exterior to said vertical pipes. 3.V In the electro deposition of metalsupon a revolving cathode of circular cross-sectiony the comblnation with such cathode of the primarily del which same may be appli-` adapted to anode arranged round the cathode 'in elements consistingof one or more anode bars, and pipes for directing the jets of electrolyte arranged in suchwise that the greatest action of the jets upon the cathode will take place l at those points on the cathode nearest the elements of the anode Where the resistance between rthe electrodes is`least and consequently the current density greatest, and means to' revolve the said cathode during electro depositionthereon.

4;. In anapparatus for electrolytically dopositing metals, the combination, with a cathode of circular cross-section, .of a series ofpipes spaced apart equidistant from one another and disposed concentrically about said cathode and provided with a series of holesorenozzles Whichdirect the ets of electrolyte issuing from said pipes in a direction tangential to the surface of the cathode, and an anodev located exteriorljT of said series of pipes.

5. ln an apparatus for eleetrolyricallydepositingflnetals, a vat, a revolnble cathode of circular cross-seetion vertically mounted in said vat, a plurality ol spaced eleelrolytedischarging pipes arranged concentricallji about and parallel to said cathode, each ol' said pipes being perforated so as to cause the electrolyte to be projected in jels against: the, cathode in a direction aj pro,\'innitel}v tangential thereto, and :1u outer series oll spaced, depending, inter-connected anode-bars also arranged concentrically about and parallel to said cathode, said bars being disposed opposite the points of impingernent ol" the jets upon the cathode.

In Witness whereof we have hereunto sel our hands in presence of two witnesses.

l HERBERT CHAMPION HARRISON.

JOSEPH DAY. Witnesses:

H. D. JAMESON, F. L. RAND. 

